WO2017208951A1 - Procédé de production de particules d'oxyde revêtues d'un composé de silicium, particules d'oxyde revêtues d'un composé de silicium et composition d'oxyde revêtue d'un composé de silicium les contenant - Google Patents

Procédé de production de particules d'oxyde revêtues d'un composé de silicium, particules d'oxyde revêtues d'un composé de silicium et composition d'oxyde revêtue d'un composé de silicium les contenant Download PDF

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WO2017208951A1
WO2017208951A1 PCT/JP2017/019469 JP2017019469W WO2017208951A1 WO 2017208951 A1 WO2017208951 A1 WO 2017208951A1 JP 2017019469 W JP2017019469 W JP 2017019469W WO 2017208951 A1 WO2017208951 A1 WO 2017208951A1
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WIPO (PCT)
Prior art keywords
silicon compound
oxide particles
coated
bond
coated oxide
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PCT/JP2017/019469
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English (en)
Japanese (ja)
Inventor
榎村眞一
本田大介
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エム・テクニック株式会社
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Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=60477555&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO2017208951(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Priority claimed from PCT/JP2016/066542 external-priority patent/WO2017061140A1/fr
Priority claimed from PCT/JP2016/083001 external-priority patent/WO2018083805A1/fr
Application filed by エム・テクニック株式会社 filed Critical エム・テクニック株式会社
Priority to US16/306,446 priority Critical patent/US11052461B2/en
Priority to JP2017531789A priority patent/JP6241700B1/ja
Priority to KR1020187033731A priority patent/KR102341564B1/ko
Priority to EP17806508.2A priority patent/EP3466882B1/fr
Priority to CN201780033017.9A priority patent/CN109195914B/zh
Publication of WO2017208951A1 publication Critical patent/WO2017208951A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
    • C01P2006/66—Hue (H*)
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/90—Other properties not specified above
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/21—Oxides
    • C03C2217/216—ZnO
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/40—Coatings comprising at least one inhomogeneous layer
    • C03C2217/42—Coatings comprising at least one inhomogeneous layer consisting of particles only
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/70—Properties of coatings
    • C03C2217/72—Decorative coatings
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/70—Properties of coatings
    • C03C2217/76—Hydrophobic and oleophobic coatings
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00—Methods for coating glass
    • C03C2218/10—Deposition methods
    • C03C2218/11—Deposition methods from solutions or suspensions
    • C03C2218/116—Deposition methods from solutions or suspensions by spin-coating, centrifugation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a method for producing silicon compound-coated oxide particles, silicon compound-coated oxide particles, and a silicon compound-coated oxide composition containing the same.
  • Patent Document 1 For such a purpose, as in Patent Document 1, by forming a layer containing oxide particles having photocatalytic activity such as titanium oxide on the product, organic substances that cause hydrophilicity and dirt due to photocatalytic activity, etc. It has been proposed to provide a self-cleaning action by decomposing. However, in such a method, organic substances or the like that cause contamination are once adhered or adsorbed on a product coating film containing oxide particles having photocatalytic activity. And since it decomposes
  • Patent Document 2 a coating film using an organic water-repellent agent has been proposed, but in those, the organic substance itself is easily decomposed with respect to ultraviolet rays and the like, and has durability.
  • an inorganic water-repellent agent having high weather resistance has been desired since it is unstable.
  • water repellency can be imparted to prevent water landing and adhesion of water droplets. Proposed.
  • the water-repellent oxide fine particles described in Patent Document 3 are hydrophobic silica, and in addition to the case where water repellency is insufficient, UV protection, which is a required characteristic other than water repellency.
  • Example 4 Since the average reflectance in the wavelength region of 300 nm to 1300 nm described in Example 4 is as very low as 5% or less, the water repellency and the ultraviolet protection ability or the near infrared protection ability are obtained as in Patent Document 3. Neither the combined material nor the composition using the material was disclosed.
  • Patent Document 5 describes particles obtained by surface-treating silica-coated metal oxide particles with a hydrophobicity-imparting material such as dimethylethoxysilane.
  • a hydrophobicity-imparting material such as dimethylethoxysilane.
  • polyglycerin triisostearate or The particles are merely treated with a hydrophobicity-imparting material in order to improve the dispersibility in an oil-based dispersion medium such as silicone oil or squalane.
  • Patent Document 5 describes that the peak observed at 1150 to 1250 cm ⁇ 1 in the infrared absorption spectrum is absorption of Si—OH bending vibration, but usually the Si—O bond. It should be attributed, and the description of Si—OH is an obvious error.
  • Patent Document 5 does not control the amount of Si—OH groups contained in the silica-coated metal oxide. That is, in Patent Document 5, as in Patent Document 3, a material having both water repellency and ultraviolet protective ability or near infrared protective ability and a composition using the same have not been disclosed.
  • the UV protection ability is such that the higher the absorbability per unit substance amount in the wavelength range of 200 nm to 380 nm, that is, the larger the “molar extinction coefficient”, the more UV light can be absorbed. It can be said. Therefore, if the molar extinction coefficient is large, a UV absorption ability similar to or higher than that of the current state can be exhibited with a small amount. Therefore, the haze value is reduced, the coated material such as a coating film, and a transparent resin, film or glass. The transparency of such transparent materials can be improved, and the aesthetics and design can be improved.
  • the near-infrared defensive ability for example, when a material that absorbs near-infrared rays is used for glass or a clear coating, half of the thermal energy derived from near-infrared absorbed by the glass or clear coating in principle is shielded. Although the other half is radiated in the direction to be shielded. For example, when heat rays are shielded by glass using a near-infrared absorber, half of the heat energy can be released outside the room, but the other half is radiated into the room, so the actual heat shielding effect is sufficient. Not. That is, for near infrared rays, there has been a demand for a material that has excellent reflection characteristics particularly in the wavelength range of 780 nm to 2500 nm, and that has no problem in terms of cost and environmental burden in mining.
  • Patent Document 6 and Patent Document 7, which disclose the invention by the applicant of the present application, are uniform using a method of depositing various nanoparticles such as iron oxide between relatively rotating processing surfaces that can approach and separate. A method for producing simple oxide nanoparticles is described.
  • Patent Document 6 describes the production of oxides and hydroxides
  • Patent Document 7 describes the production of uniform oxides.
  • materials and compositions that effectively prevent ultraviolet rays or near infrared rays and have controlled wettability such as water repellency, oil repellency, and hydrophilicity have been appealed.
  • JP 2002-286916 A Japanese Unexamined Patent Publication No. 2017-8268 JP 2010-155727 A International Publication No. 2010-007956 Pamphlet International Publication No. 2000-42112 Pamphlet Japanese Patent No. 4868558 International Publication No. 2009/008393
  • an object of the present invention is to provide a method for producing silicon compound-coated oxide particles, silicon compound-coated oxide particles, and a silicon compound-coated oxide composition using the same. That is, the ratio of the Si—OH bond contained in the silicon compound-coated metal oxide particles or the silicon compound-coated oxide particles for the purpose of maximally improving the characteristics inherent to the oxide and supplementing such characteristics.
  • the CF bond / Si—OH bond ratio which is the ratio of the CF bond to the Si—OH bond contained in, is controlled, and in addition to wettability such as water repellency, oil repellency or hydrophilicity, UV protection ability and near infrared It is an object of the present invention to provide a method for producing silicon compound-coated oxide particles having controlled color characteristics such as protective ability and silicon compound-coated oxide particles, and a composition containing the same. This utilizes the fact that the Si—OH bond ratio or the CF bond / Si—OH bond ratio contained in the silicon compound-coated oxide particles varies depending on the production method and the environmental change after production.
  • the inventor of the present application provides a ratio of Si—OH bonds or a CF bond / Si—OH bond ratio contained in silicon compound-coated oxide particles, silicon compound-coated zinc oxide particles that are the silicon compound-coated oxide particles, silicon
  • the present invention was completed by finding that the characteristics of silicon compound-coated oxide particles were improved by controlling the ratio of Si—OH bonds contained or the ratio of CF bonds / Si—OH bonds.
  • an object of the present invention is to provide a production method and silicon compound-coated oxide particles and to provide a composition containing the same.
  • the inventor of the present application determined that the ratio of the Si-OH bond contained in the silicon compound-coated oxide particles or the CF bond / Si-OH bond ratio, which is the ratio of the CF bond to the Si-OH bond, is In addition to wettability such as water repellency, oil repellency or hydrophilicity, it has been found that it has relevance to color characteristics such as transmission characteristics, absorption characteristics, reflection characteristics, and the present invention has been completed. is there.
  • the present invention is a method for producing silicon compound-coated oxide particles in which at least a part of the surface of the metal oxide particles is coated with a silicon compound, This is a method for producing silicon compound-coated oxide particles in which wettability and color characteristics are controlled by controlling the ratio of Si—OH bonds contained in the silicon compound-coated oxide particles.
  • the present invention is a method for producing a silicon compound-coated oxide particle in which at least a part of the surface of the metal oxide particle is coated with a silicon compound, wherein the silicon compound-coated oxide particle contains a CF bond,
  • the CF bond / Si—OH bond ratio which is the ratio of CF bonds to Si—OH bonds contained in the silicon compound-coated oxide particles
  • the wettability and color characteristics of the silicon compound-coated oxide particles are controlled. It is a manufacturing method.
  • the wettability is preferably water repellency or oil repellency.
  • the color characteristic is any one of reflectance, transmittance, and molar extinction coefficient.
  • the present invention also provides an infrared absorption spectrum in which the Si—OH bond ratio or the CF bond / Si—OH bond ratio contained in the silicon compound-coated oxide particles is measured using a total reflection measurement method (ATR method). It is preferably calculated by waveform separation of peaks derived from silicon compound-coated oxide particles having a wave number of 650 cm ⁇ 1 to 1300 cm ⁇ 1 in FIG.
  • ATR method total reflection measurement method
  • the present invention is a peak derived from the CF bond that is the waveform separation is preferably from wave number 1200 cm -1 in the range of 1220 cm -1 is a waveform separated peaks.
  • the functional group changing treatment is preferably fluorination treatment.
  • the fluorination treatment is preferably a trifluoromethylation treatment.
  • the ratio of Si—OH bonds contained in the silicon compound in a dispersion state in which the silicon compound-coated oxide particles are dispersed in a dispersion medium it is preferable to control the ratio of Si—OH bonds contained in the silicon compound in a dispersion state in which the silicon compound-coated oxide particles are dispersed in a dispersion medium.
  • the dispersion is a coating film, a film, or glass, and the water repellency or oil repellency and color characteristics of the silicon compound-coated oxide particles are controlled by heat-treating the dispersion. .
  • the Si—OH bond ratio it is preferable to control the Si—OH bond ratio to be low so that the average reflectance in the wavelength region from 780 nm to 2500 nm is high.
  • the present invention also provides a high average molar extinction coefficient in a wavelength region of 200 nm to 380 nm in a dispersion in which the silicon compound-coated oxide particles are dispersed in an organic solvent by controlling the Si—OH bond ratio low. It is preferable to control so that it becomes.
  • the present invention is a silicon compound-coated oxide particle in which at least a part of the surface of the metal oxide particle is coated with a silicon compound,
  • the silicon compound can change the wettability and color characteristics of the metal oxide particles by covering at least a part of the surface of the metal oxide particles.
  • the total reflection measurement method is calculated by waveform separation of the peak derived from the silicon compound-coated oxide particles 1300 cm -1 wave number 650 cm -1 in the measured infrared absorption spectrum using the above CF contained in the silicon compound-coated oxide particles Bond / Si—OH bond ratio is 0 or more and 4.5 or less, and an average molar extinction coefficient in a wavelength range of 200 nm to 380 nm is 650 L / (mol ⁇ mol ⁇ ⁇ ) in a state where the silicon compound-coated oxide particles are dispersed in a dispersion medium. cm) or more silicon compound-coated oxide particles.
  • the present invention also provides silicon compound-coated oxide particles in which the Si—OH bond ratio contained in the silicon compound-coated oxide particles is 5% or more and 70% or less.
  • the present invention is also a silicon compound-coated oxide particle in which the oxide constituting the metal oxide particle is at least one selected from the group consisting of zinc oxide, iron oxide, cerium oxide, and titanium oxide.
  • the present invention is preferably silicon compound-coated oxide particles having an average reflectance of 50% or more in the wavelength region of 780 nm to 2500 nm of the silicon compound-coated oxide particles.
  • the average transmittance for light having a wavelength of 200 nm to 380 nm is 15% or less, and the average transmittance for light having a wavelength of 380 nm to 780 nm is
  • the silicon compound-coated oxide particles are preferably 80% or more.
  • the present invention is a composite oxide particle in which the oxide particles constituting the metal oxide particles are composed of two or more elements,
  • the color characteristics of the silicon compound-coated oxide particles are in the range of 40 ⁇ L * ⁇ 95, ⁇ 35 ⁇ a * ⁇ 35, or ⁇ 35 ⁇ b * ⁇ 35 in the L * a * b * color system. Silicon compound-coated oxide particles are preferred.
  • the silicon compound is preferably a silicon compound-coated oxide particle in which the silicon compound is a silicon compound containing an amorphous silicon oxide.
  • the present invention is preferably silicon compound-coated oxide particles having a contact angle of water droplets of 110 ° or more with respect to the coated surface on which the silicon compound-coated oxide particles are coated.
  • the present invention can be implemented as a silicon compound-coated oxide composition for ultraviolet protection and water or oil repellency comprising the silicon compound-coated oxide particles.
  • the CF bond / Si—OH bond ratio which is the ratio of the Si—OH bonds contained in the silicon compound-coated oxide particles or the ratio of the CF bonds to the Si—OH bonds.
  • wettability such as oiliness or hydrophilicity
  • the CF bond / Si—OH bond ratio which is the ratio of the Si—OH bond or the CF bond to the Si—OH bond
  • the water repellency, oil repellency, hydrophilicity, etc. of the silicon compound-coated oxide particles are controlled. It is possible to strictly control the wettability and color characteristics of the silicon compound, so that it is more accurate than ever before for the growing demand for silicon compound-coated oxide particles, diversified applications, and target characteristics. The design of the composition is facilitated.
  • 3 is a STEM mapping of the silicon compound-coated zinc oxide particles obtained in Example 1-2.
  • 3 is a line analysis result of silicon compound-coated zinc oxide particles obtained in Example 1-2.
  • 4 shows IR measurement results of silicon compound-coated zinc oxide particles obtained in Example 1-2, Example 1-11, and Reference Example 1. It is the result of the waveform separation of a range of 1300 cm -1 from the wavelength 650 cm -1 in the IR measurement results of the silicon compound-coated zinc oxide particles in Reference Example 1. It is the result of the waveform separation of a range of 1300 cm -1 from the wavelength 650 cm -1 in the IR measurement results of the silicon compound-coated zinc oxide particles in Examples 1-2.
  • Example 4 is a graph of transmittance measured using a dispersion in which silicon compound-coated zinc oxide particles obtained in Example 1-2 are dispersed in propylene glycol monomethyl ether.
  • 6 is a graph of reflectance measured using the silicon compound-coated zinc oxide particles obtained in Example 1-2 and Example 1-11.
  • the state of adhesion of water droplets and the contact angle of pure water on the coating film obtained by coating the silicon compound-coated zinc oxide particles obtained in Example 1-13 and the silicon compound-coated zinc oxide particles obtained in Reference Example 1 on a glass substrate It is a measurement result.
  • the CF bond / Si—OH bond ratio which is the ratio of the Si—OH bonds contained in the silicon compound-coated oxide particles or the ratio of the CF bonds to the Si—OH bonds, is controlled.
  • the silicon compound-coated oxide particles with controlled color characteristics of reflectance, molar extinction coefficient or transmittance, and silicon according to the present invention are used for a composition intended for use in a coating film, a sealing material or a coated body, a composition intended for use in textiles such as clothing, or a clear coating film or glass required for transparency.
  • UV or near infrared is effective depending on the purpose. With a suitable composition to shield manner.
  • compositions having high transmission characteristics that is, high transparency in the visible region, it does not impair the design or aesthetics and texture over a long period of time, and is particularly suitable for coated objects that require weather resistance.
  • a silicon compound-coated metal oxide composition for water or oil repellency that can be used effectively can be provided.
  • the composition required for the transparency is used for, for example, a composition contained in glass, a transparent resin or a clear coating film itself, or a film combined with glass or a transparent resin by being attached to the glass or the transparent resin. And a paint for application to glass or transparent resin.
  • the silicon compound-coated oxide particles according to the present invention are silicon compound-coated oxide particles in which at least a part of the surface of the metal oxide particles is coated with a silicon compound, and the metal is a metal element on the chemical periodic table. Alternatively, it is a metal oxide particle containing a single metalloid element or a plurality of different elements.
  • the metal element in this invention is not specifically limited, Preferably, a bivalent or trivalent metal element is mentioned, More preferably, metal elements, such as Zn, Fe, Ce, and Ti, can be mentioned.
  • the metalloid element in the present invention is not particularly limited, but preferably metalloid elements such as Si, Ge, As, Sb, Te, Se, and Te can be exemplified.
  • metal oxide particles composed of a single metal element may be used, or composite metal oxide particles composed of a plurality of metal elements or complex metal oxides containing metal elements and metalloid elements It may be a particle.
  • the present invention is a silicon compound-coated oxide particle, when Si is included in the element constituting the metal oxide, a plurality of Si and a metal element, or a metalloid element different from Si, It must be an oxide composed of elements.
  • the silicon compound-coated oxide particles according to the present invention are not limited to those composed only of oxides.
  • the present invention can also be carried out including compounds other than oxides to the extent that they do not affect the present invention.
  • it can also be implemented as silicon compound-coated metal oxide particles in which at least part of the surface of metal oxide particles or composite metal oxide particles containing a compound other than an oxide is coated with a silicon compound.
  • Examples of compounds other than the oxides include hydroxides, nitrides, carbides, various salts such as nitrates and sulfates, and hydrates and organic solvates.
  • the silicon compound-coated oxide particles of the present invention have a controlled CF bond / Si—OH bond ratio, which is the ratio of Si—OH bonds contained in the silicon compound-coated oxide particles or the ratio of CF bonds to Si—OH bonds.
  • a plurality of particles are observed using a transmission electron microscope (TEM) or a scanning electron microscope (STEM), and energy dispersive X
  • TEM transmission electron microscope
  • STEM scanning electron microscope
  • EDS energy dispersive X
  • the abundance ratio (molar ratio) of elements other than silicon and silicon contained in one silicon compound-coated oxide particle is specified, and the average value and coefficient of variation of the molar ratio in a plurality of silicon compound-coated oxide particles.
  • silicon compound-coated oxide particles in which silicon is detected in the vicinity of the surface layer of the silicon compound-coated oxide particles in STEM mapping or line analysis are preferable.
  • the silicon compound-coated oxide particles of the present invention can be implemented as silicon compound-coated oxide particles in which at least a part of the surface of the metal oxide particles is coated with a silicon compound.
  • the photocatalytic ability generated by atomizing the oxide particles is suppressed by covering at least a part of the surface of the particles with the silicon compound.
  • chemical stability such as water resistance, acid resistance and alkali resistance can be imparted to the oxide.
  • the silicon compound-coated oxide particles of the present invention preferably contain fluorine (F) and contain CF bonds in order to control wettability such as water repellency, oil repellency or hydrophilicity. It is more preferable. More preferably, the CF bond is a fluorine or CF bond derived from a trifluoromethyl group. For the water repellency or oil repellency, the fluorine or CF bond is preferably mainly present on the surface side of the silicon compound-coated oxide particles. In the present invention, the fluorine or CF bond is coated with a silicon compound. It may be contained inside the oxide particles.
  • the critical surface tension of the trifluoromethyl group (CF 3 group) is as small as about 6 mN / m, the water repellency and oil repellency can be improved by including the CF 3 group on the surface of the particles, Further, by controlling the CF bond ratio, the color characteristics of the silicon compound-coated oxide particles such as water repellency, oil repellency, ultraviolet absorbing ability and near infrared reflecting ability can be controlled. Examples of the evaluation method for the fluorine contained in the silicon compound-coated oxide particles include the same methods as those for silicon or oxygen.
  • the water repellency or water repellency is controlled by controlling the ratio of the Si—OH bond contained in the silicon compound-coated oxide particles or the CF bond / Si—OH bond ratio, which is the ratio of the CF bond to the Si—OH bond. It controls wettability such as oiliness, and various color characteristics such as reflectance, transmittance, molar extinction coefficient, etc.
  • the Si—OH bond or the CF bond / Si—OH bond ratio is, for example, FT- It can be judged from the IR measurement result.
  • IR is an abbreviation for infrared absorption spectroscopy.
  • the Si—OH bond or the CF bond / Si—OH bond ratio may be measured by a method other than the IR measurement.
  • a method other than the IR measurement For example, X-ray photoelectron spectroscopy (XPS) ), Solid nuclear magnetic resonance (solid NMR), electron energy loss spectroscopy (EELS), and the like.
  • XPS X-ray photoelectron spectroscopy
  • solid NMR Solid nuclear magnetic resonance
  • EELS electron energy loss spectroscopy
  • the Si-OH bond ratio or the CF bond / Si-OH bond ratio contained in the silicon compound-coated oxide particles is determined from the wave number of 650 cm ⁇ 1 to 1300 cm in the infrared absorption spectrum measurement of the silicon compound-coated oxide particles.
  • peaks waveform separated from the wave number 850 cm -1 in the region of 950 cm -1 preferably waveform separated from the wave number 890 cm -1 in the region of 920 cm -1 and the peak and a peak derived from Si-OH bonds
  • the area ratio of the waveform-separated peak or the area ratio (CF bond / Si-OH bond ratio) of the peak waveform-separated by the CF bond to the area of the peak waveform-separated by the Si-OH bond.
  • the oxide particles are preferably controlled in wettability and color characteristics such as water repellency, oil repellency or hydrophilicity.
  • the CF bond for example a CF 3 group
  • vibration due to a functional group having a CF bond such as CF 2 group and CF group is considered to be detected all the wave number 1200 cm -1 in the region of 1220 cm -1
  • the peaks derived from the wave number 850 cm -1 in the Si-OH bonds which are waveform separation in the region of 950 cm -1, from the wave number 850 cm -1 in the region of 950 cm -1, as in the CF bond, the different vibration While Si-OH bonds are also contemplated to be waveform separation as a plurality of peaks, among the wave number 850 cm -1 as a representative of the Si-OH bond of the waveform separated peaks in the region of 950 cm -1, having the largest area ratio It is preferable to calculate the ratio of Si—OH bonds or the ratio of CF bonds / Si—OH bonds by using the peak as the ratio of Si—OH bonds.
  • the silicon compound that covers at least a part of the surface of the metal oxide particles may contain an amorphous silicon oxide, in particular because it becomes easy to control the ratio of Si—OH bonds.
  • the method for evaluating that the silicon compound contains amorphous silicon oxide is not particularly limited, but in addition to the confirmation of the presence of Si and O by STEM mapping and the confirmation of the presence of silicon oxide by infrared absorption spectrum. In addition, a crystal lattice is not observed at a site where Si and O are detected in a method of evaluating in combination with the fact that a peak derived from crystalline silica (SiO 2 ) is not confirmed in XRD measurement, or in TEM observation or STEM observation. The method of confirming this is mentioned.
  • the molar extinction coefficient can be calculated by the following (formula 1) from the absorbance in the UV-visible absorption spectrum measurement and the molar concentration of the substance to be measured in the measurement sample.
  • ⁇ A / (c ⁇ l) (Formula 1)
  • ⁇ is a constant specific to the substance, which is called a molar extinction coefficient, and is the absorbance of a 1 mol / L dispersion having a thickness of 1 cm. Therefore, the unit is L / (mol ⁇ cm).
  • A is the absorbance in the UV-visible absorption spectrum measurement
  • c is the molar concentration (mol / L) of the sample.
  • l is a length (optical path length) (cm) through which light is transmitted, and is usually a thickness of a cell when an ultraviolet-visible absorption spectrum is measured.
  • cm optical path length
  • a simple average of molar extinction coefficients for a plurality of wavelengths in the measurement wavelength region of wavelength 200 nm to 380 nm is calculated. Evaluated as “Coefficient”.
  • Ultraviolet rays that do not impair the aesthetics, texture, or design of the painted body or glass itself by the ability to efficiently protect the ultraviolet rays or near-infrared rays of the silicon compound-coated oxide particles whose color characteristics are also controlled. It is used for the purpose of not deteriorating the aesthetics, design, or product characteristics of the decorative or near-infrared defensive composition, the interior decorations and equipment laid with the glass containing the silicon compound-coated oxide particles of the present invention, etc. Suitable for use in transparent material compositions
  • Silicon compound-coated oxide particles for coloring A silicon compound-coated oxide particle in which at least a part of the surface of the metal oxide particle is coated with a silicon compound, wherein the metal oxide particle is composed of at least two elements selected from the metal elements or metalloid elements.
  • the silicon compound-coated oxide particles are colored, and by using the colored silicon compound-coated oxide particles in the composition, wettability and color characteristics such as water repellency, oil repellency or hydrophilicity are obtained. It is also possible to provide controlled coloring silicon compound coated oxide particle compositions.
  • the molar ratio of two kinds of metal elements or metalloid elements in metal oxide particles composed of at least two kinds of elements selected from the above metal elements or metalloid elements (M2 / M1: M1 and M2 are metal elements or metalloids, respectively)
  • the composition for coloring can be positively colored depending on the purpose. It is also suitable when used as.
  • M1 and M2, which are different elements for the purpose of coloring are not limited to complex oxides composed of two metal elements or metalloid elements.
  • M1, M2, M3... Mn can also be implemented as an oxide composed of three or more metal elements or metalloid elements.
  • the L * a * b * color system is one of uniform color spaces, and L * is a value representing brightness. The larger the value, the brighter the color.
  • a * and b * represent chromaticity.
  • the color system is not limited to the L * a * b * color system.
  • the color characteristics may be evaluated using another color system such as an XYZ system.
  • the coloring power is not too strong. Since it is possible to approximate a color that is gentle to the human eye, it is particularly suitable when used in a composition for the purpose of protecting colored UV rays.
  • the method for controlling the Si—OH bond ratio or the CF bond / Si—OH bond ratio is not particularly limited, but the above-mentioned method can be performed by changing the functional group contained in the silicon compound-coated oxide particles. It is preferable to control the Si—OH bond ratio or the CF bond / Si—OH bond ratio. Particularly when the CF bond is imparted to the silicon compound-coated oxide particles, the functional group changing treatment is preferably a fluorination treatment.
  • the functional group changing treatment is performed by a method of performing a substitution reaction, an addition reaction, an elimination reaction, a dehydration reaction, a reaction using a condensation reaction, or the like on the functional group contained in the silicon compound-coated oxide particles. It is possible to control the OH bond ratio or the CF bond / Si—OH bond ratio. In controlling the Si—OH bond ratio or the CF bond / Si—OH bond ratio, the CF bond or Si—OH bond ratio may be increased or decreased. In the present invention, by the above control, the carboxyl group (—COOH) in a carboxylic acid having a CF 3 group, such as trifluoroacetic anhydride, is added to the Si—OH bond contained in the silicon compound-coated oxide particles.
  • esterification in addition to a method using an acid anhydride, a method using a mixed acid anhydride, an acid halide or the like, or a dehydrating agent such as carbodiimide may be used.
  • dehydration can be achieved by reacting a fluorine- and hydroxyl-containing substance, or a fluorine-containing alkyl halide, aryl halide or heteroaryl halide with an Si—OH group, preferably in the presence of an acid catalyst.
  • the method of generating an ether bond between the substance having fluorine and Si or the method of generating a (thio) urethane bond by causing fluorine-containing isocyanate or thioisocyanate to act on the Si-OH, etc. It is also possible to control the —OH bond ratio or the CF bond / Si—OH bond ratio. Further, in the present invention, it is not limited to producing a new bond by causing another substance or a functional group to act directly on the Si—OH bond, for example, a carboxylic acid containing fluorine-containing carbodiimide It is also possible to control the Si—OH bond ratio or the CF bond / Si—OH bond ratio by the method of acting on the.
  • the Si—OH bond ratio or the CF bond / Si—OH bond ratio can be controlled by a method in which hydrogen peroxide or ozone acts on the oxide particles.
  • the Si compound-coated oxide particles are precipitated in the liquid, the oxide raw material liquid and the oxide precipitation solvent for precipitating the silicon compound-coated oxide particles, and the method of controlling the pH, etc. It is also possible to control the Si—OH bond ratio or the CF bond / Si—OH bond ratio.
  • the Si—OH bond ratio or the CF bond / Si—OH bond ratio can be controlled by a method of heat-treating the silicon compound-coated oxide particles.
  • the Si—OH bond ratio or the CF bond / Si—OH bond ratio is controlled by the method of heat-treating the silicon compound-coated oxide particles, it can be carried out by a dry heat treatment, or the silicon compound-coated oxide particles. It can also be carried out by heat treatment in the state of a dispersion in which is dispersed in a dispersion medium.
  • the silicon compound-coated oxide particles are dispersed in a target solvent, a substance containing a functional group is added to the dispersion, and the mixture is subjected to a treatment such as stirring to obtain the ratio of Si—OH bonds or CF bonds /
  • the Si—OH bond ratio may be controlled or the dispersion containing the silicon compound-coated oxide particles deposited by mixing the oxide raw material liquid, the oxide precipitation solvent, and the silicon compound raw material liquid is continued as it is.
  • the Si—OH bond ratio or the CF bond / Si—OH bond ratio may be controlled by performing a treatment such as stirring.
  • a device in which a dispersion device and a filtration membrane are connected is constructed, and a method such as removing impurities from the slurry containing silicon compound-coated oxide particles by a dispersion treatment for particles and a treatment by cross-flow membrane filtration is performed. It can also be carried out by changing the temperature of the slurry and the temperature of the cleaning liquid used for the cross flow.
  • the silicon compound-coated oxide particles in the present invention since the primary modification of the silicon compound-coated oxide particles, particularly the surface of each primary particle, can be uniformly modified, the silicon compound-coated oxide particles in the present invention There is an advantage that the control of the ratio of the Si—OH bond or the CF bond / Si—OH bond contained in the water and the control of water repellency or oil repellency and color characteristics can be performed more strictly and homogeneously.
  • the pH adjustment when precipitating the silicon compound-coated oxide particles may be adjusted by including a pH adjusting agent such as an acidic substance or a basic substance in at least one of the various solutions and solvents in the present invention.
  • the flow rate at the time of mixing the fluid containing the oxide raw material liquid and the fluid containing the oxide precipitation solvent may be adjusted by changing the flow rate.
  • the method for changing the functional group contained in the silicon compound-coated oxide particles according to the present invention is not particularly limited.
  • the treatment may be carried out by dispersing the silicon compound-coated oxide particles in a target solvent, adding a substance containing a functional group to the dispersion, and performing a treatment such as stirring.
  • the silicon compound-coated oxide particles may be functionalized with the fluid containing the silicon compound-coated oxide particles. You may implement by mixing the fluid containing the substance containing a group using the microreactor described in patent document 6 or patent document 7.
  • the substance containing a functional group is not particularly limited, but is a substance containing a functional group that can be substituted for the hydroxyl group contained in the oxide particles, and an acylating agent such as acetic anhydride or propionic anhydride; dimer sulfate or dimethyl carbonate And silane coupling agents such as chlorotrimethylsilane and methyltrimethoxysilane.
  • an acylating agent such as acetic anhydride or propionic anhydride
  • silane coupling agents such as chlorotrimethylsilane and methyltrimethoxysilane.
  • the ratio of Si—OH bonds can be controlled.
  • Examples of the substance containing a CF bond in the case of introducing and controlling the CF bond into silicon compound-coated oxide particles include various fluorine compounds.
  • examples of the fluorine compound include fluorine-containing compounds such as trifluoroacetic acid, trifluoromethanesulfonic acid, and anhydrides thereof, triethoxy-1H, 1H, 2H, 2H-heptadecafluorodecylsilane, Examples include silane coupling agents containing fluorine, such as trimethoxy (3,3,3-trifluoropropyl) silane, or fluorine compounds such as trifluoromethane and trifluoroethane. These listed fluorine compounds include trifluoromethyl groups. (CF 3 group) is preferable because it is contained.
  • a CF bond may be imparted by reacting these fluorine compounds with a hydroxyl group contained in the silicon compound-coated oxide particles, and the fluorine compound is allowed to act when the silicon compound-coated oxide particles are precipitated. It is also possible to produce silicon compound-coated oxide particles containing CF bonds. Furthermore, the silicon compound-coated oxide particles of the present invention can also be obtained by a method in which a gas such as trifluoromethane or trifluoroethane is allowed to act on the silicon compound-coated oxide particles or silicon compound-coated oxide particles that already contain CF bonds. It is also possible to control the Si—OH bond ratio or the CF bond / Si—OH bond ratio contained in the silicon compound-coated oxide particles.
  • the Si—OH bond ratio or the CF bond / Si—OH bond ratio can also be controlled by a method of allowing hydrogen peroxide or ozone to act on the oxide particles.
  • a method for causing hydrogen peroxide or ozone to act on oxide particles is not particularly limited.
  • the silicon compound-coated oxide particles may be dispersed in a target solvent, and a solution such as hydrogen peroxide or ozone or an aqueous solution containing them may be added to the dispersion, followed by a treatment such as stirring. You may implement by mixing the fluid containing an oxide particle, and the fluid containing hydrogen peroxide or ozone using the microreactor described in patent document 6 or patent document 7.
  • the dispersion may be implemented as a liquid dispersion in which silicon compound-coated oxide particles are dispersed in a liquid dispersion medium such as water, an organic solvent, or a resin, or a dispersion containing silicon compound-coated oxide particles. It can also be implemented as a dispersion in the form of a coating prepared using When heat treatment is performed in the form of a dispersion containing silicon compound-coated oxide particles, the aggregation of the particles can be suppressed as compared to the dry heat treatment, for example, Japanese Patent Application Laid-Open Nos. 2014-042891 and 2014-042892.
  • the silicon compound-coated oxide particles of the present invention are used for the multilayer coating film and the high-design multilayer coating film described in 1, after making the silicon compound-coated oxide particles into the multilayer coating film or the multilayer coating film, by controlling the CF bond ratio or CF bond / Si—OH bond ratio contained in the oxide particles by a method such as heat treatment, the wettability such as water repellency, oil repellency or hydrophilicity of the silicon compound-coated oxide particles and Since it is possible to control the color characteristics, it is suitable for strict control of color characteristics in addition to the reduction of the number of processes and the control of water repellency and oil repellency for a water-repellent body and glass.
  • reflected light is increased by increasing the difference between highlight and shade for a specific color.
  • the intensity of the light changes greatly depending on the observation angle, and a sense of depth and denseness is realized. Therefore, it is required to improve the transmittance for specific colors in order to enhance highlights, and to increase the difference between highlights and shades, and in particular, UV shielding such as silicon compound oxides such as clear coatings.
  • a coating film containing a substance having characteristics increases the transparency of the coating film as a dispersion of oxide particles as the molar extinction coefficient in the ultraviolet region, which is the ability of the silicon compound-coated oxide particles to absorb ultraviolet light, increases.
  • the haze value can be reduced by reducing the amount of silicon compound-coated oxide particles used.
  • the silicon compound-coated oxide particles are dispersed in glass or transparent resin to form a film, and then the functional group is changed by heat treatment or fluorination treatment to cover the silicon compound.
  • the primary particle diameter of the metal oxide particles in the silicon compound-coated oxide particles is preferably 1 nm or more and 100 nm or less, and more preferably 1 nm or more and 50 nm or less. Further, the primary particle diameter of the coated silicon compound-coated oxide particles is also preferably 1 nm or more and 100 nm or less, and more preferably 1 nm or more and 50 nm or less. Control of wettability such as water repellency, oil repellency or hydrophilicity and color characteristics can be strictly performed by the presence of CF bonds or Si—OH bonds contained in the silicon compound oxide particles mainly on the surface of the particles.
  • the silicon compound-coated oxide particles having a primary particle diameter of 100 nm or less have an increased surface area compared to silicon compound-coated oxide particles having a primary particle diameter of more than 100 nm.
  • the wettability such as water repellency, oil repellency or hydrophilicity of the silicon compound coated oxide particles by controlling the Si-OH bond ratio or CF bond / Si-OH bond ratio of the coated oxide particles It is considered that the influence on the color characteristics such as the characteristics, absorption characteristics, reflection characteristics, hue, and saturation is large.
  • the ratio of the Si—OH bond or the CF bond / Si—OH bond ratio contained in the silicon compound-coated oxide particles is controlled to be predetermined.
  • Color characteristics especially suitable for use as a coating composition, a coated body, a composition intended for use in textiles such as clothing, or a coated body, glass, transparent resin or film-like composition requiring transparency) ) Can be suitably exhibited.
  • the ratio of the average primary particle size of the silicon compound-coated oxide particles after coating with the compound to the average primary particle size of the metal oxide particles before coating is 100. It is preferably 5% or more and 190% or less. If the coating of the compound on the metal oxide particles is too thin, the silicon compound-coated oxide particles coated with the compound may not be able to exhibit the effects on water repellency or oil repellency and color characteristics, etc.
  • the average primary particle diameter of the silicon compound-coated oxide particles after coating by 10 is preferably 100.5% or more of the average primary particle diameter of the metal oxide particles.
  • the average primary particle diameter of the silicon compound-coated oxide particles after coating with the compound is 190% of the average primary particle diameter of the oxide particles. % Or less is preferable.
  • the silicon compound-coated oxide particles coated with the silicon compound according to the present invention may be core-shell type silicon compound-coated oxide particles in which the entire surface of the metal oxide particles serving as the core is uniformly coated with the compound.
  • the silicon compound-coated oxide particles are silicon compound-coated oxide particles in which a plurality of metal oxide particles are not aggregated and at least a part of the surface of a single metal oxide particle is coated with a compound. However, it may be silicon compound-coated oxide particles in which at least a part of the surface of an aggregate obtained by aggregating a plurality of metal oxide particles is coated with a compound.
  • the compound covering at least a part of the surface of the oxide is preferably a silicon compound, more preferably a silicon oxide, and even more preferably an amorphous silicon oxide.
  • a silicon compound By including an amorphous silicon oxide in the silicon compound, it is possible to strictly control color characteristics such as reflectance, transmittance, molar extinction coefficient, hue, and saturation of the silicon compound-coated oxide particles.
  • the silicon compound is a crystalline silicon oxide, it is extremely difficult to make Si—OH present, and thus it may be difficult to control the color characteristics of the present invention.
  • an oxide raw material liquid containing at least a raw material of metal oxide particles coated with a silicon compound, and an oxide for depositing the metal oxide particles A metal oxide particle is prepared by a method such as reaction, crystallization, precipitation, and coprecipitation in a mixed fluid prepared by preparing an oxide precipitation solvent containing at least a precipitation substance and mixing the oxide raw material liquid and the oxide precipitation solvent. And the mixed fluid containing the deposited metal oxide particles and a silicon compound raw material liquid containing at least a silicon compound raw material, which is a compound to be coated, are mixed to form a surface of the metal oxide particles.
  • silicon compound-coated oxide particles by coating at least a part with a silicon compound.
  • a plurality of different metal elements or metalloid elements contained in the metal oxide particles are contained together in the oxide raw material liquid. It may be contained in the oxide raw material liquid and the oxide precipitation solvent, or may be contained in both the oxide raw material liquid and the oxide precipitation solvent, or in the silicon compound raw material liquid.
  • the raw material for the silicon compound-coated oxide particles in the present invention is not particularly limited. Any method can be used as long as it becomes silicon compound-coated oxide particles by a method such as reaction, crystallization, precipitation, and coprecipitation.
  • compounds of metal elements or metalloid elements are collectively referred to as compounds.
  • the metal or metalloid containing metal element or a metalloid or a metal salt or oxide, hydroxide, hydroxide oxide, nitride, carbide, complex, organic salt, Organic complexes, organic compounds or their hydrates, organic solvates and the like can be mentioned. It is also possible to use a single metal or semi-metal.
  • the metal or metalloid salt is not particularly limited, but metal or metalloid nitrates or nitrites, sulfates or sulfites, carbonates, formates or acetates, phosphates or phosphites, hypochlorites. Examples thereof include phosphates, chlorides, oxy salts, acetylacetonate salts or hydrates thereof, organic solvates, and the like, and examples of organic compounds include metal or semimetal alkoxides. As described above, these metal or metalloid compounds may be used alone or as a mixture of two or more.
  • the metal oxide constituting the silicon compound-coated oxide particles is a plurality of different metal elements or metalloid elements
  • the main metal element is M1
  • the subordinate metal element or metalloid element is M2.
  • the molar ratio of M2 to M1 (M2 / M1) is preferably 0.01 or more and 1.00 or less.
  • examples of the raw material for the silicon compound according to the present invention include silicon oxides and hydroxides, other compounds such as silicon salts and alkoxides, and hydrates thereof.
  • silicates such as sodium silicate, phenyltrimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-trifluoropropyl-trimethoxysilane, Methacryloxypropyltriethoxysilane, tetramethoxysilane (TMOS), tetraethoxysilane (TEOS), and oligomeric condensates of TEOS, such as ethyl silicate 40, tetraisopropylsilane, tetrapropoxysilane, tetraisobutoxysilane, tetrabutoxysilane , And similar materials.
  • siloxane compounds bis (triethoxysilyl) methane, 1,9-bis (triethoxysilyl) nonane, diethoxydichlorosilane, triethoxychlorosilane, and the like may be used as a raw material for the silicon compound. These are not used only for coating the surface of the particles, but can also be used as a compound containing M1 or M2.
  • each raw material of the metal oxide particles or the silicon compound for coating is solid, each raw material is melted or mixed or dissolved in a solvent described later (including molecularly dispersed state). ) Is preferably used. Even if each raw material is a liquid or a gas, it is preferably used in a state of being mixed or dissolved in a solvent described later (including a state of molecular dispersion).
  • the oxide depositing substance is not particularly limited as long as it can deposit the silicon compound-coated oxide particle raw material contained in the oxide raw material liquid as silicon compound-coated oxide particles.
  • Basic substances can be used. It is preferable to use at least the oxide depositing substance in a state of being mixed, dissolved, and molecularly dispersed in a solvent described later.
  • Examples of basic substances include metal hydroxides such as sodium hydroxide and potassium hydroxide, metal alkoxides such as sodium methoxide and sodium isopropoxide, amine compounds such as triethylamine, diethylaminoethanol and diethylamine, and ammonia. It is done.
  • metal hydroxides such as sodium hydroxide and potassium hydroxide
  • metal alkoxides such as sodium methoxide and sodium isopropoxide
  • amine compounds such as triethylamine, diethylaminoethanol and diethylamine, and ammonia. It is done.
  • Acidic substances include inorganic acids such as aqua regia, hydrochloric acid, nitric acid, fuming nitric acid, sulfuric acid and fuming sulfuric acid, and organic acids such as formic acid, acetic acid, chloroacetic acid, dichloroacetic acid, oxalic acid, trifluoroacetic acid, trichloroacetic acid and citric acid. Examples include acids.
  • the basic substance and acidic substance can also be used for depositing silicon compound-coated oxide particles or a compound for coating.
  • solvent examples of the solvent used for the oxide raw material liquid, the oxide precipitation solvent, or the silicon compound raw material liquid include water, an organic solvent, and a mixed solvent composed of a plurality of them.
  • examples of the water include tap water, ion-exchanged water, pure water, ultrapure water, RO water (reverse osmosis water), and the organic solvents include alcohol compound solvents, amide compound solvents, ketone compound solvents, ether compounds.
  • examples include solvents, aromatic compound solvents, carbon disulfide, aliphatic compound solvents, nitrile compound solvents, sulfoxide compound solvents, halogen compound solvents, ester compound solvents, ionic liquids, carboxylic acid compounds, and sulfonic acid compounds.
  • Each of the above solvents may be used alone or in combination.
  • examples of the alcohol compound solvent include monohydric alcohols such as methanol and ethanol, polyols such as ethylene glycol and propylene glycol, and the like.
  • Dispersant etc. Various dispersants and surfactants may be used according to the purpose and necessity as long as the production of the silicon compound-coated oxide particles according to the present invention is not adversely affected. Although it does not specifically limit, As a dispersing agent and surfactant, the various commercially available products generally used, a product, or what was newly synthesize
  • Metal oxide particles coated with the silicon compound are produced by precipitation or the like.
  • the metal oxide particles are composed of a plurality of different elements M1 and M2
  • metal oxide particles composed of a metalloid element it is preferred to produce the metal oxide by substantially simultaneously depositing metal oxides composed of a plurality of different elements (M1 and M2).
  • an oxide precipitation solvent that is an aqueous solution of an alkali metal hydroxide (oxide precipitation substance) such as sodium hydroxide
  • the silicon compound-coated oxide particles are precipitated. It is necessary to mix silicon oxide-coated oxide particles by mixing an oxide precipitation solvent having a pH of 14 or higher with an oxide raw material solution having a pH of 1 to 2 or less than 1.
  • the basic oxide precipitation solvent is gradually added to the acidic oxide raw material liquid, for example.
  • the pH of the mixed solution of the oxide raw material liquid and the oxide precipitation solvent gradually changes from acidic to basic.
  • the oxide of M1 or M2 is deposited (begins to deposit), and then the oxide deposited earlier at the stage when the pH of the mixed solution has changed to the basic side by adding an oxide precipitation solvent.
  • the oxide particles composed of M1 and the oxide particles composed of M2 are deposited stepwise, such that the other oxide different from the above precipitates. In that case, it becomes difficult to produce the metal oxide particles containing both M1 and M2 inside the particles.
  • By instantaneously adjusting the mixed solution to a pH at which both the M1 oxide and the M2 oxide are precipitated it can be precipitated at the same time, so that at least M1 and M2 are present inside the particles. It is possible to prepare the preconditions for producing metal oxide particles containing both of the above.
  • Method outline-2 Metal for producing silicon compound-coated oxide particles: Method outline-2
  • the silicon compound raw material liquid is charged at a faster rate than the metal oxide particles are precipitated and then aggregated. It is important to deposit on the surface of the metal oxide particles.
  • the pH of the fluid containing the metal oxide particles and the concentration of the silicon compound raw material gradually change, and the particles are dispersed.
  • the silicon compound for coating the surface of the particles is deposited after the condition is likely to aggregate, it may be difficult to coat before aggregation to the extent that the above-described characteristics of the present invention cannot be exhibited. is there. It is preferable that the silicon compound raw material contained in the silicon compound raw material liquid is allowed to act immediately after the metal oxide particles are deposited.
  • the present inventors By controlling the Si—OH bond ratio or the CF bond / Si—OH bond ratio contained in the silicon compound-coated oxide particles, the present inventors have made the silicon compound-coated oxide particles water-repellent, oil-repellent or The inventors have found that wettability such as hydrophilicity and color characteristics can be controlled, and have completed the present invention.
  • Silicon compound-coated oxide particles in which the silicon compound is a silicon oxide, trifluoroacetic acid that gives a CF bond to the silicon compound-coated oxide particles when depositing the silicon compound-coated oxide particles, and oxides for shells The use of a substance containing a CF bond such as 3-trifluoropropyl-trimethoxysilane as a raw material is also disclosed in Japanese Patent Application No. 2016-111346, which is the basic application of this application, and this has a unique property.
  • the present inventors have further included in this silicon compound coated oxide particles as disclosed in PCT / JP2016 / 83001, another basic application of the present application.
  • the silicon oxide-coated oxide particles of the present invention substantially correspond to the silicon oxide-coated oxide particles disclosed in Japanese Patent Application No. 2016-111346, which is the basic application of the present application.
  • Examples of the method for producing silicon compound-coated oxide particles according to the present invention include, for example, producing silicon compound-coated oxide particles by using a microreactor or performing a reaction in a dilute system in a batch container. A method is mentioned.
  • an apparatus and method as described in Japanese Patent Application Laid-Open No. 2009-112892 proposed by the present applicant may be used.
  • An apparatus described in Japanese Patent Application Laid-Open No. 2009-112892 includes a stirring tank having an inner peripheral surface having a circular cross-sectional shape, and a stirring tool attached with a slight gap from the inner peripheral surface of the stirring tank.
  • the stirring tank includes at least two fluid inlets and at least one fluid outlet, and one of the fluid inlets includes a first of the reactants among the fluids to be processed.
  • the fluid to be treated is introduced into the agitation tank, and the second fluid to be treated containing one of the reactants different from the reactant is added to the first fluid from one place other than the above among the fluid inlets.
  • the fluid to be treated is introduced into the stirring tank from a different flow path, and at least one of the stirring tank and the stirring tool is rotated at a high speed with respect to the other so that the fluid to be treated is in a thin film state. Reactant contained in first treated fluid and second treated fluid It is described that three or more introduction pipes may be provided as shown in FIGS.
  • the oxide particles may be produced by using a pulverization method such as a bead mill, and after the production, a treatment may be performed in which the silicon oxide is coated on the coated oxide particles using a reaction vessel or the microreactor.
  • the silicon compound-coated oxide particles of the present invention are intended for wettability such as water repellency, oil repellency or hydrophilicity, and protection of ultraviolet rays or near infrared rays, and coloring. It can be used for a composition intended for use in textiles such as clothing, or a composition for use in a coated body, glass, transparent resin or film-like composition that requires transparency. As an example, it may be used for a coating composition or a transparent composition.
  • the composition for coating is not particularly limited, for example, a coating composition for use in various coatings such as solvent-based paints and water-based paints, cosmetics such as lipsticks, foundations, sunscreen agents, and skin.
  • the composition for transparent material it is a composition for use in a coated body, a building, a vehicle or glasses used for transparency, a transparent resin or a film-like composition, for example, glass, transparent resin or clear.
  • a composition contained in the coating film itself a film-like composition used for a film combined with glass, such as affixing to glass or transparent resin, and a paint for applying to glass.
  • the transparent resin include PMMA (polymethyl methacrylate), PC (polycarbonate), and PET (polyethylene terephthalate).
  • Silicon compound-coated oxide particle composition-2 When used as a coating, coating film, cosmetic, etc., or a material for glass or transparent resin, which is a coating composition or a composition for transparent material, the silicon compound-coated oxide particle composition according to the present invention is used for coating,
  • a method such as mixing with a composition such as a coating film or cosmetic that forms a coated body, kneading directly into glass, uncured glass, or transparent resin, and various glass films and films, or clear coating It can be used by a method such as mixing with a composition for forming a film.
  • ultraviolet or near-infrared protective coating compositions or water-repellent, water-repellent compositions that effectively shield ultraviolet rays or near-infrared rays depending on the purpose and have controlled wettability such as water repellency, oil repellency or hydrophilicity.
  • It can be made a composition for ultraviolet or near-infrared protective transparent material with controlled wettability such as oiliness or hydrophilicity.
  • the composition for UV or near-infrared protection purpose transparent material or the composition for UV or near-infrared protection purpose transparent material may be a pigment, a dye, a wetting agent, a dispersing agent, a color separation preventing agent, or a leveling agent, if necessary.
  • Viscosity modifier such as components can be further included depending on the purpose as appropriate.
  • Resin components for coating purposes include polyester resins, melamine resins, phenolic resins, epoxy resins, vinyl chloride resins, acrylic resins, urethane resins, silicone resins, and fluorine resins. Etc. may be exemplified.
  • the coating to which the coating material containing the silicon compound-coated oxide particles of the present invention is applied may be a single-layer coating material composed of a single coating composition, and Japanese Patent Application Laid-Open No. 2014-042891.
  • it may be a multi-layered coating composition composed of a plurality of coating compositions, as in the case of laminated coatings as described in JP-A-2014-042992, and is also included in coatings containing pigments. It can also be carried out, or it can be carried out by being included in a paint such as a clear paint.
  • a binder resin When the film-like composition is intended, a binder resin, a curing agent, a curing catalyst, a leveling agent, a surfactant, a silane coupling agent, an antifoaming agent, a colorant such as a pigment or a dye, if necessary. Further, an antioxidant and the like can be contained.
  • the composition for ultraviolet or near-infrared defense purpose transparent coating or the ultraviolet or near-infrared defense purpose transparent material with controlled wettability such as water repellency, oil repellency or hydrophilicity according to the present invention is composed of silicon compound-coated oxide particles.
  • the silicon compound-coated oxide particles contained in the composition may be composed of one silicon compound-coated oxide particle, and are composed of an aggregate in which a plurality of silicon compound-coated oxide particles are aggregated.
  • the size of the aggregates is preferably 100 nm or less.
  • the ultraviolet or near infrared protective purpose coating composition or the ultraviolet or near infrared protective purpose transparent material composition may be used with various color materials, or a composition for overcoating glass as a coating film. It may be a thing.
  • the ultraviolet or near infrared protective purpose coating composition or the ultraviolet or near infrared protective purpose transparent material composition with controlled wettability is a dispersion, as a dispersion medium, , Tap water, distilled water, RO water (reverse osmosis water), pure water, ultrapure water, etc., alcohol solvents such as methanol, ethanol, isopropyl alcohol; multivalents such as propylene glycol, ethylene glycol, diethylene glycol and glycerin Alcohol solvents; ester solvents such as ethyl acetate and butyl acetate; aromatic solvents such as benzene, toluene and xylene; ketone solvents such as acetone and methyl ethyl ketone; nitrile solvents such as acetonitrile; silicone oil, vegetable oil and wax Etc. These may be used alone or in combination.
  • UV or near-infrared defense coating composition having wettability such as water repellency or oil repellency according to the present invention, or a coating material used for a composition for ultraviolet or near-infrared defense purpose transparent material, or ultraviolet or near-infrared defense purpose
  • the color of the transparent material such as a film or glass used for the transparent material composition is not particularly limited, and the ultraviolet or near-infrared protective coating composition of the present invention or the ultraviolet or near-infrared protective purpose for the intended hue.
  • a composition for transparent material can be used.
  • the silicon compound-coated oxide particles of the present invention can control strict and accurate color characteristics by controlling the Si—OH bond ratio or the CF bond / Si—OH bond ratio, it is possible to protect against ultraviolet rays or near infrared rays. It is also suitable when used as a target coloring composition.
  • the composition for coating, transparent material or coloring according to the present invention contains the above-mentioned silicon compound-coated oxide particles, so that it can be used for coatings such as paints and paints used in buildings and vehicles, or in clear cases.
  • wettability such as water repellency, oil repellency or hydrophilicity is controlled, and ultraviolet rays or near infrared rays are used.
  • wettability In addition to controlling the above-mentioned wettability in painted bodies such as buildings and vehicles, it also prevents decomposition of organic substances contained in the painted body and skin damage in the human body.
  • glass used in vehicles can also control indoor ultraviolet rays that have passed through the glass, damage indoor organic materials and equipment, and increase the temperature due to near-infrared rays. And not only can it contribute to improving the transparency of glass and clear coatings to show high transmission characteristics with respect to visible light, but also the color characteristics such as hue can be strictly controlled, so Designability can be improved.
  • the color of the coated material or the transparent material is white, gray, or black, for example, a color having a whiteness of 10 to a lightness of 0 in the Munsell color system, or a red color, for example, RP in the Munsell hue ring. Colors from yellow to green, for example colors from Y to BG in the Munsell hue ring, colors from blue to purple, for example colors from B to P in the Munsell hue ring (Each including a metal color). These colors can be suitably blended in a coating composition used for a coated product of those colors. However, the present invention is not limited to this, and other hue colors may be used.
  • the coating composition or the transparent material composition containing the silicon compound-coated oxide particles of the present invention for the coating film or the top coat of the coated body exhibiting those colors, water repellency, oil repellency or
  • various compositions with controlled wettability such as hydrophilicity it can not only significantly reduce the color development of each color, but can also effectively color, for coloring to improve the design of the painted body It is also suitable as a composition.
  • Various pigments and dyes can be used as the pigments and dyes included in the coating, transparent material, or coloring composition as necessary. For example, all pigments and dyes registered in the color index can be used. it can. Among them, for example, C.I. I.
  • Pigments and dyes classified as Pigment Green, and pigments constituting a blue color include C.I. I. Pigments and dyes classified as Pigment Blue, and C.I. I. Pigments and dyes classified as Pigment White, and C.I. I. Pigments and dyes classified as Pigment Yellow, and pigments and dyes constituting red are represented by C.I. I. Pigments and dyes classified as Pigment Red, C.I. I. Pigment Violet and C.I. I. Examples thereof include pigments and dyes classified as Pigment Orange. More specifically, C.I. I. Pigment Red 122 and C.I. I. Quinacridone pigments such as CI Pigment Violet 19 and C.I. I. Pigment Red 254 and C.I. I.
  • Diketopyrrolopyrrole pigments such as C.I. Pigment Orange 73; I. Pigment Red 150 and C.I. I. Naphthol pigments such as C.I. Pigment Red 170 and C.I. I. Pigment Red 123 and C.I. I. Perylene pigments such as CI Pigment Red 179 and C.I. I. And azo pigments such as Pigment Red 144.
  • These pigments and dyes may be used alone or in combination.
  • the composition containing the silicon compound-coated oxide particles of the present invention can be blended alone with a coating composition, a transparent material, or a coloring composition without being mixed with the pigment and dye.
  • sample preparation for TEM observation and sample preparation for STEM observation A part of the wet cake sample of silicon compound-coated oxide particles obtained in the examples was dispersed in propylene glycol monomethyl ether, and the obtained dispersion was dropped onto a collodion film and dried to prepare a sample for TEM observation or STEM A sample for observation was used.
  • silicon compound-coated oxide particles obtained in Reference Examples described later a part of the wet cake sample of the obtained silicon compound-coated oxide particles was dispersed in propylene glycol, and the resulting dispersion was used. Furthermore, it diluted with isopropyl alcohol (IPA) 100 times, and the obtained dispersion liquid was dripped at the collodion film
  • IPA isopropyl alcohol
  • TEM-EDS analysis Transmission electron microscope and energy dispersive X-ray analyzer: TEM-EDS analysis
  • TEM-EDS analysis For observation and quantitative analysis of silicon compound-coated oxide particles by TEM-EDS analysis, a transmission electron microscope equipped with an energy dispersive X-ray analyzer, JED-2300 (manufactured by JEOL Ltd.), JEM-2100 (Japan) Electronics Co., Ltd.) was used.
  • the acceleration voltage was set to 80 kV and the observation magnification was set to 25,000 times or more.
  • the particle diameter was calculated from the distance between the maximum circumferences of the silicon compound-coated oxide particles observed by TEM, and the average value (average primary particle diameter) of the results of measuring the particle diameter for 100 particles was calculated.
  • the molar ratio of the element components constituting the silicon compound-coated oxide was calculated by TEM-EDS, and the average value of the results of calculating the molar ratio for 10 or more particles was calculated.
  • STEM-EDS analysis For the mapping and quantification of elements contained in silicon compound-coated oxide particles by STEM-EDS analysis, an atomic resolution analytical electron microscope equipped with an energy dispersive X-ray analyzer, Centurio (manufactured by JEOL Ltd.), JEM-ARM200F (manufactured by JEOL Ltd.) was used. The observation conditions were an acceleration voltage of 80 kV, an observation magnification of 50,000 times or more, and analysis using a beam diameter of 0.2 nm in diameter.
  • X-ray diffraction measurement For X-ray diffraction (XRD) measurement, a powder X-ray diffraction measurement device EMPYREAN (Spectris Co., Ltd. PANalytical Division) was used. The measurement conditions were: measurement range: 10 to 100 [° 2 ⁇ ] Cu counter cathode, tube voltage 45 kV, tube current 40 mA, scanning speed 0.3 ° / min. XRD measurement was performed using the dry powder of silicon compound-coated oxide particles obtained in each Example and Reference Example.
  • FT-IR measurement For the FT-IR measurement, a Fourier transform infrared spectrophotometer, FT / IR-6600 (manufactured by JASCO Corporation) was used. The measurement conditions are a resolution of 4.0 cm ⁇ 1 and an integration count of 1024 using the ATR method in a nitrogen atmosphere. Waveform separation of the peak of 1300 cm -1 wave number 650 cm -1 in the IR spectra, using spectral analysis program supplied with the control software of the FT / IR-6600, so that the residual square sum is 0.01 or less Curve fitting. It measured using the dry powder of the silicon compound covering oxide particle obtained by the Example and the reference example.
  • the molar extinction coefficient is obtained by measuring the absorption spectrum, calculating the molar extinction coefficient at each measurement wavelength from the absorbance obtained from the measurement results and the oxide concentration of the dispersion, the measurement wavelength on the horizontal axis, and the molar extinction coefficient on the vertical axis. It was set as the graph which described. For the measurement, a liquid cell having a thickness of 1 cm was used. In addition, the molar extinction coefficient at a plurality of measurement wavelengths from 200 nm to 380 nm was simply averaged to calculate the average molar extinction coefficient.
  • the reflection spectrum is measured from 200 nm to 2500 nm, the sampling rate is 2.0 nm, the measurement speed is medium speed, the measurement method is a double beam photometry method, and total reflection measurement is performed to measure regular reflection and diffuse reflection. It was.
  • a standard white plate product name: Spectralon (trademark), manufactured by Labsphere) was used for background measurement (baseline setting) when measuring powder.
  • the reflection spectrum was measured using the dry powder of silicon compound-coated oxide particles obtained in each Example. For a specific wavelength region, the reflectance at a plurality of measurement wavelengths was simply averaged to obtain an average reflectance. Hue and saturation are based on the results of reflection spectrum measurement.
  • the color system is L * a * b * color system
  • the visual field is 2 (deg)
  • the light source is D65-2
  • the color matching function is JIS Z 8701: 1999
  • saturation C ((a * ) 2 + (b * ) 2 ) 1 / Calculation was performed using the equation ( 2 ).
  • Example 1 hereinafter, in Example 1, it describes about the silicon compound covering zinc oxide particle which coat
  • Claremix product name: CLM-2.2S, manufactured by M Technique Co., Ltd.
  • an oxide precipitation solvent liquid A
  • an oxide raw material liquid liquid B
  • a silicon compound raw material liquid C liquid
  • each component of the oxide raw material liquid was prepared using Claremix at a preparation temperature of 40 ° C. and a rotor rotation speed of 20000 rpm.
  • the mixture was homogeneously mixed by stirring for a minute to prepare an oxide raw material liquid. Moreover, based on the prescription
  • a silicon compound raw material liquid was prepared by mixing homogeneously.
  • MeOH is methanol (manufactured by Gordo Co., Ltd.)
  • EG is ethylene glycol (manufactured by Kishida Chemical Co., Ltd.)
  • KOH is potassium hydroxide (Nippon Soda Co., Ltd.) company Ltd.)
  • TEOS is tetraethyl orthosilicate (Wako Pure Chemical Industries, Ltd.)
  • ZnO zinc oxide (manufactured by Kanto Chemical Co., Inc.)
  • Zn (NO 3) 2 ⁇ 6H 2 O is zinc nitrate hexahydrate (Kanto chemical Co., Ltd.)
  • Co (NO 3) 2 ⁇ 6H 2 O is cobalt nitrate hexahydrate (manufactured by Kanto chemical Co., Inc.), M
  • the prepared oxide raw material liquid, oxide precipitation solvent, and silicon compound raw material liquid were mixed using the fluid treatment apparatus described in Patent Document 7 by the present applicant.
  • the fluid treatment device described in Patent Document 7 is the device described in FIG. 1B of the publication, and the openings d20 and d30 of the second and third introduction portions are formed in a ring shape.
  • a disc having a concentric ring shape surrounding the central opening of the processing surface 2 was used.
  • the liquid A an oxide precipitation solvent or an oxide precipitation solvent is introduced between the processing surfaces 1 and 2 from the first introduction part d1, and while the processing part 10 is operated at a rotation speed of 1130 rpm, the liquid B
  • the oxide raw material liquid or the oxide precipitation solvent As the oxide raw material liquid or the oxide precipitation solvent, the other liquid different from the liquid sent as the liquid A is introduced between the processing surfaces 1 and 2 from the second introduction part d2, and the oxide raw material liquid
  • An oxide precipitation solvent was mixed in the thin film fluid, and zinc oxide particles serving as a core were precipitated between the processing surfaces 1 and 2.
  • a silicon compound raw material liquid was introduced as a C liquid between the processing surfaces 1 and 2 from the third introduction part d3 and mixed with a mixed fluid containing zinc oxide particles serving as a core in the thin film fluid.
  • a silicon compound is deposited on the surface of the zinc oxide particles as a core, and a discharge liquid containing silicon compound-coated zinc oxide particles (hereinafter, silicon compound-coated zinc oxide particle dispersion) is applied between the processing surfaces 1 and 2 of the fluid treatment apparatus. It was discharged.
  • the discharged silicon compound-coated zinc oxide particle dispersion was recovered in the beaker b via the vessel v.
  • Table 2 shows the operating conditions of the fluid treatment apparatus, the average primary particle diameter calculated from the TEM observation result of the obtained silicon compound-coated zinc oxide particles, and the F / Si / Zn molar ratio calculated from the TEM-EDS analysis. It shows with the calculated value calculated from the prescription of liquid, B liquid, and C liquid, and an introduction flow rate.
  • a zinc oxide particle that is a core for coloring purposes is a composite oxide containing a metal element or metalloid element other than zinc
  • a metal element or metalloid element different from zinc is defined as M2 and M3
  • F The molar ratio of / Si / (Zn + M2 + M3) is shown.
  • the introduction temperature (liquid feeding temperature) and the introduction pressure (liquid feeding pressure) of the liquid A, liquid B and liquid C shown in Table 2 are sealed introduction paths (first introduction part) leading to the processing surfaces 1 and 2.
  • d1, the second introduction part d2, and the third introduction part d3) were measured by using a thermometer and a pressure gauge, and the introduction temperature of the liquid A shown in Table 2 was the first introduction
  • the introduction temperature of the liquid B is the actual temperature of the liquid B under the introduction pressure in the second introduction part d2
  • the introduction temperature of the liquid C Is the actual temperature of the liquid C under the introduction pressure in the third introduction part d3.
  • a model D-51 pH meter manufactured by HORIBA, Ltd. was used for pH measurement. Before introducing the liquid A, liquid B and liquid C into the fluid treatment apparatus, the pH was measured at room temperature. Moreover, it is difficult to measure the pH of the mixed fluid immediately after mixing the oxide raw material liquid and the oxide precipitation solvent, and the pH immediately after mixing the fluid containing the zinc oxide particles serving as the core and the silicon compound raw material liquid. The pH of the silicon compound-coated zinc oxide particle dispersion liquid discharged from the apparatus and collected in the beaker b was measured at room temperature.
  • a dry powder and a wet cake sample were prepared from the silicon compound-coated zinc oxide particle dispersion liquid discharged from the fluid treatment apparatus and collected in the beaker b.
  • a production method it is carried out in accordance with a conventional method of this kind of treatment, and the discharged silicon compound-coated zinc oxide particle dispersion is recovered, the silicon compound-coated zinc oxide particles are settled to remove the supernatant, and then purified water
  • the silicon compound-coated zinc oxide particles are washed by repeating washing with 100 parts by mass and sedimentation three times, and then washing with pure water and sedimentation three times to finally obtain the silicon compound.
  • a part of the wet cake of coated zinc oxide particles was dried at ⁇ 0.10 MPaG at 25 ° C. for 20 hours to obtain a dry powder. The rest was used as a wet cake sample.
  • Examples 1-1 to 1-3 are metal oxides for the purpose of changing the CF bond / Si—OH bond ratio, which is the ratio of Si—OH bonds or the ratio of Si—OH bonds to CF bonds.
  • the temperature at which the fluid containing a silicon compound and a substance containing a CF bond (fluorination treatment agent) was allowed to act on the metal oxide particles was changed.
  • the type of the fluorination agent was changed from that in Example 1-1.
  • Examples 1-7 to 1-10 for the purpose of coloring the silicon compound-coated zinc oxide particles, not only zinc (Zn) but also cobalt (Co), iron (Fe ), Manganese (Mn) or aluminum (Al).
  • Example 1-1 to Example 1-10 the ratio of Si—OH bonds and CF bonds contained in the silicon compound-coated zinc oxide particles was controlled between the relatively rotating processing surfaces that can approach and separate.
  • the silicon compound-coated zinc oxide particles obtained in Reference Example 1 were allowed to act on the silicon compound-coated zinc oxide particles by using trifluoroacetic anhydride. Was fluorinated.
  • the silicon compound-coated zinc oxide particles obtained in Reference Example 1 were introduced into methyl ethyl ketone so as to be 0.1% by mass as silicon compound-coated zinc oxide particles, and
  • Clairemix which is a high-speed rotary dispersion emulsifier (Product name: CLM-2.2S, manufactured by M Technique Co., Ltd.)
  • the mixture is homogeneously mixed and dispersed by stirring for 30 minutes at a preparation temperature of 30 ° C. and a rotor rotational speed of 20000 rpm.
  • a particle dispersion was prepared.
  • a dry powder and a wet cake sample were prepared from the fluorinated silicon compound-coated zinc oxide particle dispersion.
  • a production method it is carried out according to a conventional method of this type of treatment, and in the fluorinated silicon compound-coated zinc oxide particle dispersion, the fluorinated silicon compound-coated zinc oxide particles are settled to remove the supernatant, Thereafter, washing with 100 parts by mass of methyl ethyl ketone and sedimentation were repeated three times, and then washing with methanol and sedimentation were repeated three times to wash the fluorinated silicon compound-coated zinc oxide particles.
  • Example 1-1 The silicon compound-coated zinc oxide particles of Example 1-1 were heat-treated using an electric furnace as a treatment for changing functional groups contained in the silicon compound of the silicon compound-coated zinc oxide particles.
  • the heat treatment conditions were as follows: Example 1-1: Untreated, Example 1-12: 30 minutes at 100 ° C., Example 1-13: 30 minutes at 200 ° C., Example 1-14: 60 at 200 ° C. Min, Example 1-15: 90 min at 200 ° C.
  • Example 1-1 The silicon compound-coated zinc oxide particles of Example 1-1 were heat-treated using an electric furnace while flowing trifluoromethane gas as a treatment for changing the functional group contained in the silicon compound of the silicon compound-coated zinc oxide particles.
  • the treatment conditions were as follows: Example 1-16: 100 ° C. for 60 minutes (gas flow: 2 L / min), Example 1-17: 200 ° C. for 60 minutes (gas flow: 2 L / min), Example 1 18: 60 minutes at 200 ° C. (gas flow: 5 L / min).
  • the silicon compound-coated zinc oxide particles of Reference Example 1 were heat-treated using an electric furnace as a treatment for changing functional groups contained in the silicon compound of the silicon compound-coated zinc oxide particles.
  • the heat treatment conditions were as follows: Reference Example 1: Untreated, Example 1-19: 100 ° C. for 30 minutes, Example 1-20: 200 ° C. for 30 minutes, Example 1-21: 200 ° C. for 60 minutes, Example 1-22: 90 minutes at 200 ° C.
  • FIG. 1 shows the mapping result of the silicon compound-coated zinc oxide particles obtained in Example 1-2 using STEM
  • FIG. 2 shows the result of line analysis at the position where the broken line is applied in the BF image of FIG.
  • (a) is a bright field image (BF image)
  • (b) is silicon (Si)
  • (c) is zinc (Zn)
  • (d) is oxygen (O)
  • (e) is fluorine.
  • FIG. 2 is a result of line analysis at the position where a broken line is given in the BF image of FIG. 1, and shows the atomic% (mol%) of the element detected in the line portion from the end of the particle to the end. It is.
  • FIG. 1 shows the mapping result of the silicon compound-coated zinc oxide particles obtained in Example 1-2 using STEM
  • FIG. 2 shows the result of line analysis at the position where the broken line is applied in the BF image of FIG.
  • (a) is a bright field image (BF image)
  • (b) is silicon (Si)
  • Example 2 oxygen, silicon and fluorine were detected up to both ends of the analysis range in the line analysis, but zinc was detected only to the inside of a few nm from the end of the particle. It can be seen that the surfaces of the particles are coated with a silicon compound containing silicon oxide and a compound containing fluorine. As can be seen in FIGS. 1 and 2, the silicon compound-coated zinc oxide particles obtained in Example 1-2 were observed as zinc oxide particles in which the entire particles were covered with a compound containing a silicon compound and fluorine. . For the silicon compound-coated oxide particles obtained in Example 1-1 and Examples 1-3 to 1-22, the same STEM mapping and line analysis results as in Example 1-2 were obtained.
  • the entire zinc oxide particles were not covered with silicon oxide, and a part of the surface of the zinc oxide particles was covered with a silicon compound containing silicon oxide. Silicon compound-coated zinc oxide particles were also confirmed. In this invention, it can implement as a silicon compound covering oxide particle which coat
  • FIG. 3 shows IR measurement results of the silicon compound-coated zinc oxide particles obtained in Example 1-2, Example 1-11 and Reference Example 1 measured by the ATR method.
  • the IR measurement results of the silicon compound-coated oxide particles obtained in Example 1-2 and Example 1-11 were 1000 cm ⁇ 1 in comparison with the IR measurement result of the silicon compound-coated zinc oxide obtained in Reference Example 1.
  • a new peak was observed near 1300 cm ⁇ 1 from the vicinity.
  • a peak derived from a carbonyl group was observed in the vicinity of 1673 cm ⁇ 1 , and the silicon compound-coated zinc oxide particles obtained in Reference Example 1 were observed. It was found that an ester bond was formed by allowing trifluoroacetic anhydride to act on the.
  • FIG. 4 shows silicon compound-coated zinc oxide particles obtained in Reference Example 1
  • FIG. 5 shows silicon compound-coated zinc oxide particles obtained in Example 1-2
  • FIG. 6 shows silicon compound obtained in Example 1-11. respectively, for coated zinc oxide particles are shown the results of waveform separation for the region of 1300 cm -1 wave number 650 cm -1 in the IR spectrum.
  • the peaks are identified in the vicinity of 1205cm -1 Can be attributed to a CF bond
  • the silicon compound-coated zinc oxide particles obtained in Example 1-2 and Example 1-11 are silicon compound-coated zinc oxide particles containing a CF bond. confirmed.
  • the fluorinated silicon compound-coated zinc oxide particles obtained in Example 1-2 and Example 1-11 were separated in waveform from the silicon compound-coated zinc oxide particles obtained in Reference Example 1. It can be seen that the ratio of Si—OH bonds to the total peak area is lowered.
  • the fluorinated silicon compound-coated zinc oxide particles obtained in Example 1-2 and Example 1-11 are more particles. It was found that the Si—OH bond ratio contained was low and the CF bond ratio was high.
  • the area of the Si-OH bond of the area ratio of the total area of the peaks waveform separation for the region of 1300 cm -1 wave number 650 cm -1 in the IR spectrum (Si-OH Ratio [%])
  • CF bond / Si—OH bond ratio which is the area ratio (Si—OH ratio [%]) of the Si—OH bond to the ratio (CF ratio [%])
  • the water repellency of the silicon compound-coated zinc oxide particles It is possible to control wettability and color characteristics such as oil repellency or hydrophilicity.
  • FIG. 7 shows the XRD measurement results of the silicon compound-coated zinc oxide particles obtained in Example 1-2. As seen in FIG. 7, in the XRD measurement, only the peak derived from ZnO was detected. That is, it was confirmed that the silicon compound containing silicon oxide confirmed in the STEM and IR measurement was an amorphous silicon compound. Similar XRD measurement results were obtained for Example 1-1 and Examples 1-3 to 1-22.
  • the fluorinated silicon compound-coated zinc oxide particles obtained in Example 1-2, Example 1-3, Example 1-5 and Example 1-11 are dispersed in propylene glycol monomethyl ether (PGME).
  • PGME propylene glycol monomethyl ether
  • the result of the molar extinction coefficient in the dispersed liquid and the result of the molar extinction coefficient in the dispersion obtained by dispersing the silicon compound-coated zinc oxide particles obtained in Reference Example 1 in propylene glycol (PG) are shown.
  • Reference Example 1 not the fluorinated silicon compound-coated zinc oxide particles but the hydrophilicity of the particles is high because the Si—OH bond ratio exceeds 70%, so that the dispersion medium is propylene glycol.
  • Example 1-2, 1-3, 1-5 and 1-11 the water repellency is increased by fluorination, so the dispersion medium is changed to propylene glycol monomethyl ether.
  • the molar extinction coefficient was measured with the primary particle size and the dispersed particle size being equivalent.
  • the silicon compound-coated zinc oxide particles obtained in Reference Example 1 were dispersed in propylene glycol monomethyl ether, the dispersion stability was very low, and the particles settled immediately after the end of the dispersion treatment.
  • the silicon compound-coated zinc oxide particles obtained in Examples 1-3, 1-5, and 1-11 were dispersed in propylene glycol, they settled immediately after the dispersion treatment was completed. This is because of this.
  • the dispersion medium of the dispersion for measuring the molar extinction coefficient and transmittance is propylene glycol monomethyl ether, and for all the reference examples, the dispersion medium is propylene glycol. .
  • the silicon compound-coated zinc oxide particles obtained in Example 1-2, Example 1-3, Example 1-5, and Example 1-11 are better than Reference Example 1. It can be seen that the molar extinction coefficient in the wavelength range of 200 nm to 380 nm is improved. That is, it was found that the average molar extinction coefficient in the wavelength range of 200 nm to 380 nm is changed by changing the ratio of Si—OH bonds contained in the particles. In the above Examples 1-1 to 1-22, the average molar extinction coefficient in the wavelength range of 200 nm to 380 nm is 650 L / (mol ⁇ cm) or more, and the light ray in the ultraviolet range is from 200 nm to 380 nm. It was found to have the ability to effectively absorb.
  • FIG. 9 shows the transmission spectrum of the dispersion obtained by dispersing the silicon compound-coated zinc oxide particles propylene glycol monomethyl ether obtained in Example 1-2.
  • the average transmittance in the wavelength range of 200 nm to 380 nm is 15% or less, and in the wavelength range of 380 nm to 780 nm, it is 80% or more. It is a dispersion having a high permeation performance and can be suitably used for various compositions.
  • FIG. 10 shows the reflectance measurement results of the silicon compound-coated zinc oxide particles obtained in Example 1-2 and Example 1-11. As seen in FIG. 10, since the average reflectance in the wavelength range of 780 nm to 2500 nm is 50% or more, it was found that the film has high reflection characteristics with respect to light rays in the near infrared region.
  • the dispersion obtained by dispersing the silicon compound-coated zinc oxide particles obtained in Example 1-13 in propylene glycol monomethyl ether was applied to a glass substrate with a spin coater (Mikasa Sakai MS-A100) at 200 ° C. Vacuum drying ( ⁇ 0.1 MPaG) for 2 hours was performed to obtain a silicon compound-coated zinc oxide particle coating film. Further, a dispersion obtained by dispersing the silicon compound-coated zinc oxide particles obtained in Reference Example 1 in propylene glycol was applied to a glass substrate with a spin coater (MIKASA MS-A100), and the resulting mixture was applied at 25 ° C. for 20 hours. Was vacuum-dried (-0.1 MPaG) to obtain a silicon compound-coated zinc oxide particle coating film.
  • the contact angle of pure water or castor oil was measured for the obtained coating film using a contact angle meter (LSE-B100) manufactured by Asumi Giken Co., Ltd.
  • the calculation method was calculated using the ⁇ / 2 method.
  • a photograph at the time of measurement using pure water is shown in FIG.
  • the contact angle of Example 1-13 was 159.7 °, and the contact angle of Reference Example 1 was 95.1 °. From this, it was found that the silicon compound obtained in Example 1-13 had improved water repellency.
  • Table 3 shows Si-OH bond ratio, CF bond ratio, CF bond / Si-OH bond for the silicon compound-coated zinc oxide particles obtained in Examples 1-1 to 1-22 and Reference Example 1. The ratio, average reflectance, average molar extinction coefficient, average transmittance, L * value, b * value, c * value, hue, saturation, and contact angle are shown.
  • the silicon compound-coated zinc oxide particles of the present invention have a CF bond / Si—OH bond ratio of 0 to 4.5 and a Si—OH bond ratio of 5% to 70%.
  • the average molar extinction coefficient in the wavelength region of 200 nm to 380 nm is 650 L / (mol ⁇ cm) or more in a state where the oxide particles are dispersed in the dispersion medium. Further, as seen in Examples 1-7 to 1-10, it was found that coloring can be achieved by combining elements such as Fe, Co, Mn, and Al with zinc oxide particles. From these, by controlling the Si—OH bond or the CF bond / Si—OH bond ratio contained in the silicon compound-coated zinc oxide particles, the average molar extinction coefficient in the wavelength range of 200 nm to 380 nm, the wavelength of 780 nm to 2500 nm.
  • the average reflectance in the range and the wettability such as water repellency, oil repellency or hydrophilicity can be controlled. More specifically, by controlling the Si—OH bond ratio contained in the silicon compound-coated zinc oxide particles to be low and controlling the CF bond / Si—OH bond ratio to be high, the average moles in the wavelength range of 200 nm to 380 nm. It was found that the light absorption coefficient, the average reflectance in the wavelength range of 780 nm to 2500 nm, and the water repellency or oil repellency can be improved.
  • Example 2 describes silicon compound-coated iron oxide particles in which at least a part of the surface of iron oxide particles is coated with a silicon compound as oxide particles. Except for the production conditions shown in Tables 4 and 5, production was performed under the same conditions as in Examples 1-1 to 1-6.
  • MeOH is methanol (made by Gordo Co., Ltd.)
  • TEOS is tetraethyl orthosilicate (made by Wako Pure Chemical Industries, Ltd.)
  • Fe (NO 3 ) 3 9H 2 O is iron nitrate nonahydrate (manufactured by Kanto Chemical Co., Inc.)
  • NaOH is sodium hydroxide (manufactured by Kanto Chemical Co., Ltd.)
  • NMP is N-methyl-2-pyrrolidone (manufactured by Kishida Chemical Co., Ltd.)
  • Treatment agent 1 is triethoxy-1H, 1H, 2H, 2H-heptadecafluorodecylsilane (manufactured by Tokyo Chemical Industry Co., Ltd.)
  • Table 6 shows the Si—OH bond ratio, the CF bond ratio, and the CF bond / Si—OH bond ratio for the silicon compound-coated iron oxide particles obtained in Examples 2-1 to 2-6 and Reference Example 2. , Average reflectance, average molar extinction coefficient, average transmittance, and contact angle.
  • Example 2 as in Example 1, the water-repellent property or the water-repellent property was controlled by controlling the Si—OH bond or CF bond / Si—OH bond ratio contained in the silicon compound-coated oxide particles. It was found that oil repellency and color characteristics can be controlled.
  • the silicon compound-coated iron oxide particles have a CF bond / Si—OH bond ratio of 0 to 4.5 and a Si—OH bond ratio of 5% to 70%.
  • Silicon compound-coated iron oxide particles having an average molar extinction coefficient of 1500 L / (mol ⁇ cm) or more in a wavelength range of 200 nm to 380 nm in a state where the coated iron oxide particles are dispersed in a dispersion medium are preferable.
  • Example 3 describes silicon compound-coated cerium oxide particles in which at least a part of the surface of cerium oxide particles is coated with a silicon compound as oxide particles. Except for the production conditions shown in Tables 7 and 8, the production conditions were the same as those in Examples 1-1 to 1-6.
  • MeOH is methanol (made by Gordo Co., Ltd.)
  • TEOS is tetraethyl orthosilicate (made by Wako Pure Chemical Industries, Ltd.)
  • Ce (NO 3 ) 3 6H 2 O is cerium nitrate hexahydrate (Kanto Chemical Co., Ltd.)
  • NaOH is sodium hydroxide (Kanto Chemical Co., Ltd.)
  • NMP is N-methyl-2-pyrrolidone (Kishida Chemical Co., Ltd.)
  • Treatment agent 1 is triethoxy-1H, 1H, 2H, 2H-heptadecafluorodecylsilane (manufactured by Tokyo Chemical Industry Co., Ltd.)
  • fluorination treatment agent 2 is trimethoxy (3,3,3-trifluoropropyl) silane (Tokyo) Kasei Kogyo Co., Ltd.)
  • fluorination treatment agent 3 is trifluoroacetic
  • Example 2 As a result of STEM mapping and line analysis and an XRD measurement result, the same result as in Example 1 was obtained. As for the XRD measurement result, only a peak derived from CeO 2 was detected.
  • Table 9 shows Si-OH bond ratio, CF bond ratio, CF bond / Si-OH bond for the silicon compound-coated cerium oxide particles obtained in Example 3-1 to Example 3-6 and Reference Example 3. The ratio, average reflectance, average molar extinction coefficient, average transmittance, and contact angle are shown. As can be seen from Table 9, in Example 3 as well as in Examples 1 and 2, by controlling the Si—OH bond ratio or the CF bond / Si—OH bond ratio contained in the silicon compound-coated oxide particles. It was found that water repellency or oil repellency and color characteristics can be controlled.
  • the CF bond / Si—OH bond ratio is 0 or more and 4.5 or less, and the Si—OH bond ratio is 5% or more and 70% or less.
  • the silicon compound-coated cerium oxide particles having an average molar extinction coefficient of 3500 L / (mol ⁇ cm) or more in a wavelength range of 200 nm to 380 nm in a state where the silicon compound-coated cerium oxide particles are dispersed in a dispersion medium are preferable. .
  • Example 4 describes silicon compound-coated titanium oxide particles in which at least a part of the surface of titanium oxide particles is coated with a silicon compound as oxide particles. It was created under the same conditions as in Example 1-1 to Example 1-6 except that the conditions at the time of production were Table 10 and Table 11. In addition, about the substance shown by the chemical formula and abbreviated symbol of Table 10, MeOH is methanol (made by Gordo Co., Ltd.), TEOS is tetraethyl orthosilicate (made by Wako Pure Chemical Industries, Ltd.), TiOSO 4 ⁇ nH 2 O.
  • Is titanyl sulfate n hydrate (manufactured by Kanto Chemical Co., Ltd., used as TiOSO 4 ⁇ 2H 2 O), NaOH is sodium hydroxide (manufactured by Kanto Chemical Co., Ltd.), and NMP is N-methyl-2-pyrrolidone (Kishida Chemical Co., Ltd.), fluorination treatment agent 1 is triethoxy-1H, 1H, 2H, 2H-heptadecafluorodecylsilane (manufactured by Tokyo Chemical Industry Co., Ltd.), and fluorination treatment agent 2 is trimethoxy (3, 3, 3- Trifluoropropyl) silane (manufactured by Tokyo Chemical Industry Co., Ltd.), fluorination treatment agent 3 is trifluoroacetic anhydride (manufactured by Kanto Chemical Co., Ltd.), fluoride As the treating agent 4, trifluoromethanesulfonic anhydride (manufactured by Kanto Chemical
  • Example 2 As a result of STEM mapping and line analysis and an XRD measurement result, the same results as in Example 1 were obtained. In the XRD measurement result, only a peak derived from TiO 2 was detected.
  • Table 12 shows the Si—OH bond ratio, the CF bond ratio, and the CF bond / Si—OH bond ratio for the silicon compound-coated titanium oxide particles obtained in Examples 4-1 to 4-6 and Reference Example 4. , Average reflectance, average molar extinction coefficient, average transmittance, and contact angle. As can be seen from Table 12, also in Example 4, in the same manner as in Examples 1 to 3, by controlling the ratio of Si—OH bonds or the CF bond / Si—OH bond ratio contained in the silicon compound-coated oxide particles. It was found that water repellency or oil repellency and color characteristics can be controlled.
  • the CF bond / Si—OH bond ratio is 0 or more and 4.5 or less, and the Si—OH bond ratio is 5% or more and 70% or less.
  • the silicon compound-coated titanium oxide particles having an average molar extinction coefficient of 4000 L / (mol ⁇ cm) or more in a wavelength range of 200 nm to 380 nm in a state where the silicon compound-coated titanium oxide particles are dispersed in a dispersion medium are preferable. .
  • Example 5 As Example 5, except that the apparatus described in Japanese Patent Application Laid-Open No. 2009-112892 and the mixing / reaction method of liquid A, liquid B and liquid C were used, the same conditions as in Example 1 were applied, so that the silicon compound coating was achieved. Zinc oxide particles were prepared.
  • the apparatus described in Japanese Patent Application Laid-Open No. 2009-112892 uses the apparatus shown in FIG. 1 of the same publication, and the inner diameter of the stirring tank is 80 mm, the outer end of the stirring tool, the inner peripheral side surface of the stirring tank, and the gap are 0 The rotational speed of the stirring blade was 7200 rpm.
  • Table 13 shows the silicon compound-coated zinc oxide particles obtained in Example 5 and Reference Example 5.
  • the coefficient, average transmittance and contact angle are shown.
  • Si—OH contained in the silicon compound-coated oxide particles was also used as in Examples 1 to 4. It was found that the water repellency or oil repellency and color characteristics can be controlled by controlling the bond ratio or the CF bond / Si—OH bond ratio.

Abstract

La présente invention concerne un procédé de production de particules d'oxyde revêtues d'un composé de silicium, qui sont des particules d'oxyde métallique revêtues sur au moins une partie de leurs surfaces avec un composé de silicium; ce procédé est caractérisé par le contrôle des propriétés de mouillage et des caractéristiques de couleur en contrôlant le rapport des liaisons Si-OH incluses dans les particules d'oxyde revêtues de composé de silicium. Grâce à cette invention, il est possible de fournir des particules d'oxyde revêtues d'un composé de silicium, de contrôler les propriétés de mouillage telles que l'hydrophobicité, l'oléophobie ou l'hydrophilie, et de contrôler une caractéristique de couleur choisie parmi la réflectance, le coefficient d'extinction molaire et la transmission.
PCT/JP2017/019469 2016-06-02 2017-05-25 Procédé de production de particules d'oxyde revêtues d'un composé de silicium, particules d'oxyde revêtues d'un composé de silicium et composition d'oxyde revêtue d'un composé de silicium les contenant WO2017208951A1 (fr)

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US16/306,446 US11052461B2 (en) 2016-06-02 2017-05-25 Method of producing silicon compound coated oxide particles, silicon compound coated oxide particles, and silicon compound coated oxide composition containing the same
JP2017531789A JP6241700B1 (ja) 2016-06-02 2017-05-25 ケイ素化合物被覆酸化物粒子の製造方法
KR1020187033731A KR102341564B1 (ko) 2016-06-02 2017-05-25 규소 화합물 피복 산화물 입자의 제조 방법, 규소 화합물 피복 산화물 입자 및 그것을 포함하는 규소 화합물 피복 산화물 조성물
EP17806508.2A EP3466882B1 (fr) 2016-06-02 2017-05-25 Procédé de production de particules d'oxyde revêtues d'un composé de silicium, particules d'oxyde revêtues d'un composé de silicium et composition d'oxyde revêtue d'un composé de silicium les contenant
CN201780033017.9A CN109195914B (zh) 2016-06-02 2017-05-25 覆盖有硅化合物的氧化物粒子及其制造方法、和含有其的覆盖有硅化合物的氧化物组合物

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JP2016111346 2016-06-02
JP2016-111346 2016-06-02
PCT/JP2016/066542 WO2017061140A1 (fr) 2015-10-05 2016-06-03 Particules d'oxydes métalliques et procédé pour la production de ces dernières
JPPCT/JP2016/066542 2016-06-03
PCT/JP2016/083001 WO2018083805A1 (fr) 2016-11-07 2016-11-07 Procédé de production d'une particule d'oxyde revêtue d'un composé de silicium ayant des caractéristiques de couleur contrôlées, particule d'oxyde revêtue d'un composé de silicium, et composition de revêtement contenant une particule d'oxyde revêtue d'un composé de silicium
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